JPH0647734B2 - Deposited film formation method - Google Patents
Deposited film formation methodInfo
- Publication number
- JPH0647734B2 JPH0647734B2 JP61040333A JP4033386A JPH0647734B2 JP H0647734 B2 JPH0647734 B2 JP H0647734B2 JP 61040333 A JP61040333 A JP 61040333A JP 4033386 A JP4033386 A JP 4033386A JP H0647734 B2 JPH0647734 B2 JP H0647734B2
- Authority
- JP
- Japan
- Prior art keywords
- deposited film
- gas
- film
- gaseous
- film forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 50
- 230000015572 biosynthetic process Effects 0.000 title claims description 36
- 239000007789 gas Substances 0.000 claims description 153
- 239000000758 substrate Substances 0.000 claims description 88
- 229910052736 halogen Inorganic materials 0.000 claims description 35
- 150000002367 halogens Chemical class 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 30
- 239000007800 oxidant agent Substances 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 26
- 230000001590 oxidative effect Effects 0.000 claims description 21
- -1 silane compound Chemical class 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 230000005281 excited state Effects 0.000 claims description 9
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910000078 germane Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910000083 tin tetrahydride Inorganic materials 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 239000010408 film Substances 0.000 description 220
- 230000003287 optical effect Effects 0.000 description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 239000000460 chlorine Substances 0.000 description 16
- 238000007664 blowing Methods 0.000 description 13
- 238000002003 electron diffraction Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 9
- 239000010453 quartz Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000013626 chemical specie Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001120 nichrome Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 229910020328 SiSn Inorganic materials 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 101150097381 Mtor gene Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
- H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic System
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Description
【発明の詳細な説明】 〔発明の属する技術分野〕 本発明は、機能性膜、殊に半導体デバイス、電子写真用
の感光デバイス、光学的画像入力装置の光入力センサー
デバイス等の電子デバイスの用途に有用な機能性堆積膜
の形成法に関する。Description: TECHNICAL FIELD The present invention relates to the use of functional films, particularly electronic devices such as semiconductor devices, electrophotographic photosensitive devices, and optical input sensor devices for optical image input devices. The present invention relates to a method for forming a functionally deposited film useful for the above.
従来、半導体膜、絶縁膜、光導電膜、磁性膜或いは金属
膜等の非晶質乃至多結晶質の機能性膜は、所望される物
理的特性や用途等の観点から個々に適した成膜方法が採
用されている。Conventionally, an amorphous or polycrystalline functional film such as a semiconductor film, an insulating film, a photoconductive film, a magnetic film, or a metal film is individually formed from the viewpoint of desired physical characteristics or intended use. The method has been adopted.
例えば、必要に応じて、水素原子（Ｈ）やハロゲン原子
（Ｘ）等の補償剤で不対電子が補償された非晶質や多結
晶質の非単結晶シリコン（以後「ＮＯＮ−Si（Ｈ，
Ｘ）」と略記し、その中でも殊に非晶質シリコンを示す
場合には「Ａ−Si（Ｈ，Ｘ）」、多結晶質シリコンを示
す場合には「poly−Si（Ｈ，Ｘ）」と記す。）膜等のシ
リコン堆積膜（尚、俗に言う微結晶シリコンは、Ａ−Si
（Ｈ，Ｘ）の範疇のものであることは云うまでもな
い。）の形成には、真空蒸着法、プラズマCVD法、熱CVD
法、反応スパッタリング法、イオンプレーテイング法、
光ＣＶＤ法などが試みられており、一般的には、プラズ
マＣＶＤ法が広く用いられ、企業化もされている。For example, amorphous or polycrystalline non-single-crystal silicon (hereinafter referred to as "NON-Si (H)" in which unpaired electrons are compensated with a compensating agent such as a hydrogen atom (H) or a halogen atom (X), if necessary. ，
X) ”, and in particular,“ A-Si (H, X) ”indicates amorphous silicon, and“ poly-Si (H, X) ”indicates polycrystalline silicon. Is written. ) A film such as a silicon deposited film (the so-called microcrystalline silicon is A-Si
It goes without saying that it belongs to the category of (H, X). ) Is formed by vacuum deposition method, plasma CVD method, thermal CVD method.
Method, reactive sputtering method, ion plating method,
The optical CVD method and the like have been tried, and generally, the plasma CVD method is widely used and has been commercialized.
而乍ら、従来から一般化されているプラズマＣＶＤ法に
よるシリコン堆積膜の形成に於ての反応プロセスは、従
来のＣＶＤ法に比較してからなり複雑であり、その反応
機構も不明な点が少なくない。又、その堆積膜の形成に
ついてのパラメーターは多く、例えば、基体温度、導入
ガスの流量と比、形成時の圧力、高周波電力、電極構
造、反応容器の構造、排気の速度、プラズマ発生方式な
どがあり、そしてこれらの多くのパラメータの組み合わ
せによつているため、時にはプラズマが不安定な状態に
なり、形成された堆積膜に著しい悪影響を与えることが
少なくなかった。そのうえ、装置特有のパラメータを装
置ごとに選定しなければならず、したがって製造条件を
一般化することがむずかしいというのが実状であつた。However, the reaction process in forming a silicon deposited film by the plasma CVD method which has been generalized in the past is more complicated than that in the conventional CVD method, and the reaction mechanism is unclear. Not a few. Further, there are many parameters for forming the deposited film, for example, the substrate temperature, the flow rate and ratio of the introduced gas, the pressure at the time of formation, the high frequency power, the electrode structure, the structure of the reaction vessel, the exhaust speed, the plasma generation method, etc. Yes, and due to the combination of many of these parameters, the plasma was sometimes in an unstable state, often having a significant adverse effect on the deposited film formed. In addition, it is difficult to generalize the manufacturing conditions because it is necessary to select a device-specific parameter for each device.
他方、シリコン堆積膜として、電気的、光学特性を各用
途毎に十分に満足させ得るものを発現させるためには、
現状ではプラズマＣＶＤ法によつて形成することが最良
とされている。On the other hand, in order to develop a silicon deposited film that can sufficiently satisfy electrical and optical characteristics for each application,
At present, it is considered best to form by the plasma CVD method.
ところで、シリコン堆積膜の応用乃至用途によつては、
大面積化、膜厚均一性、膜品質の均一性を十分満足させ
て再現性のある量産化が望まれるところ、従来のプラズ
マＣＶＤ法によるシリコン堆積膜の形成においては、量
産装置に多大な設備投資が必要となり、またその量産の
為の管理項目も複雑になり、管理許容幅も狭く、装置の
調整も微妙であることから、これらのことが、今後改善
すべき問題点として指摘されている。By the way, depending on the application or use of the deposited silicon film,
It is desirable to mass-produce with sufficient reproducibility by sufficiently satisfying the requirements for large area, film thickness uniformity, and film quality uniformity. Since investment is required, management items for mass production are complicated, management allowance is narrow, and device adjustment is delicate, these are pointed out as problems to be improved in the future. .
又、プラズマＣＶＤ法の場合には、成膜される基体の配
されている成膜空間に於いて高周波或いはマイクロ波等
によって直接プラズマを生成している為に、発生する電
子や多数のイオン種が成膜過程に於いて膜にダメージを
与え膜品質の低下、膜品質の不均一化の要因となってい
る。Further, in the case of the plasma CVD method, since plasma is directly generated by a high frequency wave or a microwave in the film formation space in which the substrate to be formed is arranged, electrons and a large number of ion species are generated. Causes damage to the film during the film formation process and causes deterioration of film quality and nonuniformity of film quality.
この点の改良として提案されている方法には、間接プラ
ズマＣＶＤ法がある。A method proposed as an improvement on this point is an indirect plasma CVD method.
該間接プラズマＣＶＤ法は、成膜空間から離れた上流位
置にてマイクロ波等によつてプラズマを生成し、該プラ
ズマを成膜空間まで輸送することで、成膜に有効な化学
種に選択的に使用出来る様に計ったものである。In the indirect plasma CVD method, a plasma is generated by a microwave or the like at an upstream position away from the film formation space, and the plasma is transported to the film formation space to selectively select a chemical species effective for film formation. It is designed to be used for.
而乍ら、斯かるプラズマＣＶＤ法でも、プラズマの輸送
が必須であることから、成膜に有効な化学種の寿命が長
くなければならず、したがつて、使用できるガス種には
制限があり、したがって種々の堆積膜が得られないこ
と、また、プラズマを発生する為に多大なエネルギーを
要すること、更には、成膜に有効な化学種の生成及び量
が簡便な管理下に本質的に置かれないこと等の問題点が
残存している。However, even in such a plasma CVD method, the transport of plasma is indispensable, and therefore the lifetime of the chemical species effective for film formation must be long, and therefore, the usable gas species are limited. Therefore, various deposited films cannot be obtained, a large amount of energy is required to generate plasma, and the generation and amount of chemical species effective for film formation are essentially controlled under simple control. There are still problems such as not being placed.
プラズマＣＶＤ法に対して、光ＣＶＤ法は、成膜時と膜
品質にダメージを与えるイオン種や電子が発生しないと
いう点で有利ではあるが、光源にそれ程多くの種類がな
いこと、光源の波長も紫外に片寄つていること、工業化
する場合には大型の光源とその電源を要すること、光源
からの光を成膜空間に導入する窓が成膜時に被膜されて
しまう為に成膜中に光量の低下、強いては、光源からの
光の成膜空間に入射されなくなるという問題点がある。In contrast to the plasma CVD method, the photo CVD method is advantageous in that it does not generate ion species or electrons that damage the film quality and film quality, but there are not so many types of light sources, and the wavelength of the light source is large. Is also deviated to the ultraviolet, a large light source and its power source are required for industrialization, and the window that introduces the light from the light source into the film formation space is coated during film formation. However, there is a problem that the light from the light source does not enter the film forming space.
上述の如く、シリコン堆積膜の形成に於ては、幾多の問
題点が未解決のまま残存しているところ、一方では、そ
の実用機能な特性、均一性を維持させながら低コストな
装置で省エネルギー化を計つて量産化できる形成方法を
開発することが切望されている。As described above, in forming a silicon deposited film, many problems remain unsolved. On the other hand, while maintaining its practical function characteristics and uniformity, a low-cost device saves energy. It is earnestly desired to develop a forming method that can be mass-produced by measuring the cost.
これ等のことは、他の機能性膜、例えば窒化シリコン
膜、炭化シリコン膜、酸化シリコン膜においても各々同
様のことが云える。The same applies to other functional films such as a silicon nitride film, a silicon carbide film, and a silicon oxide film.
本発明の目的は、上述した従来の堆積膜形成法に於ける
問題点を排除すると同時に、従来の形成方法によらない
新規な滞積膜形成法を提供することにある。An object of the present invention is to eliminate the above-mentioned problems in the conventional deposited film forming method and to provide a new accumulated film forming method which does not depend on the conventional forming method.
本発明の他の目的は、省エネルギー化を計ると同時に膜
品質の管理が容易で大面積に亘つて均一特性の滞積膜が
得られる滞積膜形成法を提供することにある。Another object of the present invention is to provide a method for forming a deposited film capable of achieving energy saving, easily controlling the film quality, and obtaining a deposited film having a uniform property over a large area.
本発明の更に別の目的は、生産性、量産性に優れ、高品
質で電気的、光学的、半導体的等の物理特性に優れた膜
が簡便にして効率的に得られる堆積膜形成法を提供する
ことにある。Still another object of the present invention is to provide a deposited film forming method which is excellent in productivity and mass productivity, and which can easily and efficiently obtain a film having high quality and excellent physical properties such as electrical, optical and semiconductor properties. To provide.
本発明者らは、先に、堆積膜形成用の原料物質と、該原
料物質に酸化作用する性質を有する気体状ハロゲン系酸
化剤を、反応空間に導入して化学的に接触せしめて励起
状態の前駆体を生成し、該前駆体を堆積膜構成要素の供
給源として基体上に堆積膜を形成せしめる方法を提供
し、該方法は従来の堆積膜形成法の各種問題点を排除す
るものであって、従来の堆積膜形成法に於けるように各
種パラメーターを厳密に制御することなくして、且つま
たエネルギーを多くは必要とせずして簡便にして効率的
に所望の堆積膜の形成を可能にするものであるが、本発
明者らは、該方法をより有効なものにすべく更に研究を
重ねた結果以下のところが判明した。The present inventors first introduced into a reaction space a raw material substance for forming a deposited film and a gaseous halogen-based oxidant having a property of oxidizing the raw material substance, and chemically contacting the raw material substance to produce an excited state. And a method for forming a deposited film on a substrate by using the precursor as a source of a deposited film constituent, the method eliminating various problems of the conventional deposited film forming method. Therefore, it is possible to easily and efficiently form a desired deposited film without strictly controlling various parameters as in the conventional deposited film forming method and without requiring much energy. However, as a result of further studies to make the method more effective, the present inventors have found the following.
即ち、先づ、前記方法にあつて、反応空間に、堆積膜形
成用の気体状原料物質と該原料物質に酸化作用する性質
を有する気体状ハロゲン系酸化剤に加えて、水素ガスを
接触的に導入してそれらを化学的に接触させた場合、前
駆体と共に原子状水素及び原子状ハロゲンが生成し、こ
れら原子上水素及び原子状ハロゲンが形成される堆積膜
の特性に影響を与えること。That is, first, in the above method, hydrogen gas is catalytically added to the reaction space in addition to the gaseous raw material for forming a deposited film and the gaseous halogen-based oxidant having a property of oxidizing the raw material. Atomic hydrogen and atomic halogen are generated together with the precursor when introduced into the above and chemically contacted with each other, and the above-mentioned atomic hydrogen and atomic halogen affect the characteristics of the deposited film.
成膜空間における基本近傍では、前駆体の衝突により形
成される堆積膜の表面は、その際原子状水素が存在する
と、それが作用して再配列され、それにより堆積膜の特
性が改善されること。In the vicinity of the base in the deposition space, the surface of the deposited film formed by the collision of the precursors, when atomic hydrogen is present, is rearranged by the action of atomic hydrogen, thereby improving the properties of the deposited film. thing.
ただし、原子状ハロゲンが多く存在すると形成される堆
積膜の特性にはむしろ悪影響を与えてしまうこと。However, if a large amount of atomic halogen is present, it will rather adversely affect the characteristics of the deposited film.
こうした知見を基にして本発明者らが研究を勧めた結
果、前記の反応空間に於て生成する原子状水素と原子状
ハロゲンについては以下のような反応上の関係が存在す
ることがわかつた。As a result of the present inventors recommending research based on these findings, it was found that there is the following reaction relationship between atomic hydrogen and atomic halogen generated in the reaction space. .
即ち、 Ｈ2＋Ｘ２→ＨＸ＋・Ｘ＋・Ｈ Ｈ2＋・Ｘ→ＨＸ＋・Ｈ・ Ｈ＋Ｘ２→ＨＸ＋・Ｘ 〔正し、Ｘはハロゲン原子を示す。〕 そして、上記反応は発熱反応であつて、成膜空間では進
行するものであるところ、導入する水素ガスの量を調節
して、生成する原子状ハロゲンの量をコントロールして
やると、上述した原子状水素による堆積膜の特性の改善
が顕著になされることがわかつた。That is, H 2 + X 2 → HX + · X + · H H 2 + · X → HX + · H · H + X 2 → HX + · X [correctly, X represents a halogen atom. The above reaction is an exothermic reaction and proceeds in the film formation space.However, if the amount of hydrogen gas introduced is adjusted to control the amount of atomic halogen produced, It was found that the characteristics of the deposited film were significantly improved by hydrogen.
本発明は、こうした本発明者らが見い出した事実に基い
て完成した、前述した従来の堆積膜形成法における各種
問題点を排除して上述の本発明の目的を達成するもので
あつて、堆積膜形成用の気体状原料物質と、水素ガスと
該原料物質に酸化作用をする性質を有する気体状ハロゲ
ン系酸化剤と、を反応空間内に導入して化学的に接触さ
せることで前駆体及び原子状水素を生成し、該前駆体を
堆積膜構成要素の供給源として成膜空間内にある基体上
に堆積膜を形成することを特徴とするものである。The present invention has been completed based on the facts found by the present inventors, and achieves the above-mentioned object of the present invention by eliminating various problems in the above-described conventional deposited film forming method. By introducing a gaseous raw material for film formation, a hydrogen gas and a gaseous halogen-based oxidant having a property of oxidizing the raw material into the reaction space and chemically contacting them, the precursor and The present invention is characterized in that atomic hydrogen is generated, and the deposited film is formed on the substrate in the film formation space by using the precursor as a supply source of the deposited film constituent element.
そして、前記水素ガスの量は、使用される気体状原料物
質の量及び気体状ハロゲン系酸化剤の量により、そして
また実用性の観点及び経済性の観点にも考慮をはらつて
適宜決められるものであるが、一般には容量比で、使用
される気体状のハロゲン系酸化剤の量１に対し好ましく
は０．０１以上、より好ましくは０．１以上とされる。
なお、その上限はやはり容量比で、使用される気体状ハ
ロゲン系酸化剤１に対し100である。The amount of the hydrogen gas is appropriately determined depending on the amount of the gaseous raw material used and the amount of the gaseous halogen-based oxidant, and also in consideration of the practicality and the economical efficiency. However, in general, the volume ratio is preferably 0.01 or more, and more preferably 0.1 or more with respect to the amount of the gaseous halogen-based oxidizing agent used.
The upper limit of the volume ratio is 100 with respect to the gaseous halogen-based oxidizing agent 1 used.
前記構成の本発明の堆積膜形成法によれば、省エネルギ
ー化と同時に大面積化、膜厚均一性、膜品質の均一性を
十分満足させて管理の簡素化と量産化を図り、量産装置
に多大な設備投資も必要とせず、またその量産の為の管
理項目も明確になり、管理許容幅も広く、装置の調整も
簡単になる。According to the deposited film forming method of the present invention having the above-described configuration, energy saving, large area, uniform film thickness, and uniform film quality are sufficiently satisfied to simplify management and mass production, and to be a mass production apparatus. It does not require a large capital investment, the management items for mass production are clarified, the management allowance range is wide, and the adjustment of the device is easy.
本発明の堆積膜形成法に於いて、使用される堆積膜形成
用の気体状原料物質は、気体状ハロゲン系酸化剤との化
学的接触により酸化作用をうけるものであり、目的とす
る堆積膜の種類、特性、用途等によつて所望に従つて適
宜選択される。本発明に於いては、上記の気体状原料物
質及び気体状ハロゲン系酸化剤は、化学的接触をする際
に気体状とされるものであれば良く、通常の場合は、気
体でも液体でも固体であつても差支えない。In the deposited film forming method of the present invention, the gaseous raw material used for forming the deposited film is subjected to an oxidative action by chemical contact with a gaseous halogen-based oxidant, and the desired deposited film is obtained. It is appropriately selected according to the desired type, characteristics, application, etc. In the present invention, the above-mentioned gaseous raw material and gaseous halogen-based oxidizing agent may be those that are made gaseous when they are chemically contacted, and in the usual case, they are gas, liquid or solid. But it doesn't matter.
堆積膜形成用の原料物質あるいはハロゲン系酸化剤が液
体又は固体である場合には、Ar、He、N2等のキヤリアー
ガスを使用し、必要に応じては熱も加えながらバブリン
グを行なつて反応空間に堆積膜形成用の原料物質及びハ
ロゲン系酸化剤を気体状として導入する。When the raw material for forming the deposited film or the halogen-based oxidizer is liquid or solid, use a carrier gas such as Ar, He, or N 2 and perform bubbling while adding heat if necessary. A raw material for forming a deposited film and a halogen-based oxidizing agent are introduced into the reaction space in a gaseous state.
この際、上記気体状原料物質及び気体状ハロゲ系酸化剤
の分圧及び混合比は、キヤリアーガスの流量あるいは堆
積膜形成用の原料物質及び気体状ハロゲン系酸化剤の蒸
気圧を調節することにより設定される。At this time, the partial pressure and the mixing ratio of the gaseous raw material and the gaseous halogen-based oxidant are adjusted by adjusting the flow rate of the carrier gas or the vapor pressure of the raw material for forming the deposited film and the gaseous halogen-based oxidant. Is set.
本発明において使用される堆積膜形成用の原料物質とし
ては、例えば、半導体性或いは電気的絶縁性のシリコン
堆積膜やゲルマニウム堆積膜等のテトラヘドラル系の堆
積膜を得るのであれば、直鎖状、及び分岐状の鎖状シラ
ン化合物、環状シラン化合物、鎖状ゲルマニウム化合物
等が有効なものとして挙げることができる。As the raw material for forming the deposited film used in the present invention, for example, if a tetrahedral-based deposited film such as a semiconductor or electrically insulating silicon deposited film or a germanium deposited film is obtained, a straight chain, Further, a branched chain silane compound, a cyclic silane compound, a chain germanium compound and the like can be mentioned as effective ones.
具体的には、直鎖状シラン化合物としてはSiH2n+2（ｎ
＝１，２，３，４，５，６，７，８）、分岐状鎖状シラ
ン化合物としては、SiH3SiH（SiH3）SiH2SiH3、鎖状ゲ
ルマン化合物としては、GemH2m＋２（ｍ＝１，２，３，
４，５）等が挙げられる。この他、例えばスズの堆積膜
を作成するのであればSnH4等の水素化スズを有効な原料
物質として挙げることが出来る。Specifically, as the linear silane compound, SiH 2n + 2 (n
= 1,2,3,4,5,6,7,8), SiH 3 SiH (SiH 3 ) SiH 2 SiH 3 as a branched chain silane compound, and GemH 2 m + 2 (as a chain germane compound. m = 1, 2, 3,
4, 5) and the like. In addition, tin hydride such as SnH 4 can be cited as an effective raw material if, for example, a deposited film of tin is formed.
勿論、これ等の原料物質は１種のみならず２種以上混合
して使用することも出来る。Of course, these raw material substances may be used alone or in combination of two or more.
本発明に於いて使用されるハロゲン系酸化剤は、反応空
間内に導入される際気体状とされ、同時に反応空間内に
導入される堆積膜形成用の気体状原料物質に化学的接触
だけで効果点に酸化作用をする性質を有するもので、
F2、Cl2、Br2、I2等のハロゲンガス、発生期状態の弗
素、塩素、臭素等が有効なものとして挙げることが出来
る。The halogen-based oxidant used in the present invention is gasified when introduced into the reaction space, and at the same time, only by chemical contact with a gaseous raw material for forming a deposited film which is introduced into the reaction space. It has the property of oxidizing the effect point,
Halogen gas such as F 2 , Cl 2 , Br 2 and I 2 , nascent fluorine, chlorine, bromine and the like can be mentioned as effective ones.
これ等のハロゲン系酸化剤は気体状で、前記の堆積膜形
成用の原料物質の気体と共に所望の流量と供給圧を与え
られて反応空間内に導入されて前記原料物質と混合衝突
することで化学的接触をし、前記原料物質に酸化作用を
して励起状態の前駆体を含む複数種の前駆体を効率的に
生成する。生成される励起状態の前駆体及び他の前駆体
は、少なくともそのいずれか１つが形成される堆積膜の
構成要素の供給源として働く。These halogen-based oxidants are gaseous, and are introduced into the reaction space at a desired flow rate and supply pressure together with the gas of the raw material for forming the deposited film, and are mixed and collided with the raw material. The precursor is chemically contacted with the raw material to oxidize the raw material to efficiently generate a plurality of precursors including a precursor in an excited state. The excited state precursors and other precursors that are produced serve as a source of constituents of the deposited film, at least one of which is formed.
生成される前駆体は分解して又は反応して別の励起状態
の前駆体又は別の励起状態にある前駆体になつて、或い
は必要に応じてエネルギーを放出はするがそのままの形
態で成膜空間に配設された基体表面に触れることで三次
元ネツトワーク構造の堆積膜が作成される。The produced precursor decomposes or reacts to become a precursor in another excited state or a precursor in another excited state, or releases energy as necessary, but forms a film as it is. A deposited film having a three-dimensional network structure is created by touching the surface of the substrate arranged in the space.
励起されるエネルギーレベルとしては、前記励起状態の
前駆体がより低いエネルギーレベルにエネルギー遷移す
る、又は別の化学種に変化する過程に於いて発光を伴う
エネルギーレベルであることが好ましい。斯かるエネル
ギーの遷移に発光を伴なう励起状態の前駆体を含め活性
化された前駆体が形成されることで本発明の堆積膜形成
プロセスは、より効率的に、そしてより省エネルギーで
進行し、膜全面に亘つて均一でより良好な物理特性を有
する堆積膜が形成される。The excited energy level is preferably an energy level accompanied by light emission in the process of energy transition of the precursor in the excited state to a lower energy level or change to another chemical species. The deposition film formation process of the present invention proceeds more efficiently and with less energy consumption by forming activated precursors including excited state precursors accompanied by light emission in such energy transition. A deposited film having uniform and better physical properties is formed over the entire surface of the film.
本発明に於いては、堆積膜形成プロセスが円滑に進行
し、高品質で所望の物理特性を有する膜が形成される可
く、成膜因子としての、原料物質及びハロゲン系酸化剤
の種類と組み合せ、これ等の混合比、水素ガスの流量、
混合時の圧力、流量、成膜空間内圧、ガスの流型、成膜
温度（基体温度及び雰囲気温度）が所望に応じて適宜選
択される。これ等の成膜因子は有機的に関連し、単独で
決定されるものではなく相互関連の下に夫々に応じて決
定される。本発明に於いて、反応空間に導入される体積
膜形成用の気体状原料物質と気体状ハロゲン系酸化剤と
の量の割合は、上記成膜因子の中関連する成膜因子との
関係に於いて適宜所望に従つて決められるが、導入流量
比で、好ましくは、１／２０〜１００／１が適当であ
り、より好ましくは１／５〜５０／１とされるのが望ま
しい。In the present invention, the deposited film forming process proceeds smoothly, and a film having high quality and desired physical properties can be formed. Combination, mixing ratio of these, flow rate of hydrogen gas,
The pressure at the time of mixing, the flow rate, the internal pressure of the film forming space, the gas flow pattern, and the film forming temperature (base temperature and atmosphere temperature) are appropriately selected as desired. These film forming factors are organically related, and are not determined individually but are determined according to each other under mutual relation. In the present invention, the ratio of the amounts of the gaseous source material for forming a volumetric film and the gaseous halogen-based oxidant introduced into the reaction space depends on the relationship between the above film forming factors and the related film forming factors. In this case, the introduction flow rate ratio is preferably 1/20 to 100/1, and more preferably 1/5 to 50/1, although it can be determined as desired.
反応空間に導入される際の混合時の圧力としては前記気
体状原料物質及び前記水素ガスと前記気体状ハロゲン系
酸化剤との科学的接触を確立的により高める為には、よ
り高い方が良いが、反応性を考慮して適宜所望に応じて
最適値を決定するのが良い。前記混合時の圧力として
は、上記の様にして決められるが、夫々の導入時の圧力
として、好ましくは１×１０-7気圧〜１０気圧より、よ
り好ましくは１×１０-6気圧〜３気圧とされるのが望ま
しい。The pressure at the time of mixing when introduced into the reaction space is preferably higher in order to enhance scientific contact between the gaseous raw material and the hydrogen gas and the gaseous halogen-based oxidant. However, it is preferable to determine the optimum value as appropriate in consideration of reactivity. The pressure at the time of mixing is determined as described above, but the pressure at the time of introducing each is preferably from 1 × 10 −7 atm to 10 atm, more preferably from 1 × 10 −6 atm to 3 atm. Is desirable.
成膜空間内の圧力、即ち、その表面に成膜される基体が
配設されている空間内の圧力は、反応空間に於いて生成
される励起状態の前駆体（以下、前駆体Ｅという。）及
び場合によつて該前駆体より派生的に生ずる前駆体（以
下、前駆体Ｄという。）が成膜に効果的に寄与する様に
適宜所望に応じて設定される。The pressure in the film-forming space, that is, the pressure in the space where the substrate on which the film is to be formed is disposed is in the excited state in the reaction space (hereinafter referred to as precursor E). ) And in some cases a precursor derived from the precursor (hereinafter referred to as precursor D) is appropriately set as desired so as to effectively contribute to film formation.
成膜空間の内圧力は、成膜空間が反応空間と開放的に連
続している場合には、堆積膜形成用の基体原料物質及び
水素ガスと気体状ハロゲン系酸化剤との反応空間での導
入圧及び流量との関連に於いて、例えば差動排気或い
は、大型の排気装置の使用等の工夫を加えて調整するこ
とが出来る。The internal pressure of the film formation space is such that, when the film formation space is open and continuous with the reaction space, the base material for forming the deposited film and the reaction space between the hydrogen gas and the gaseous halogen-based oxidant are used. The relationship between the introduction pressure and the flow rate can be adjusted by, for example, adding differential exhaust or using a large exhaust device.
或いは、反応空間と成膜空間の連結部のコンダクタンス
が小さい場合には、成膜空間に適当な排気装置を設け、
該装置の排気量を制御することで成膜空間の圧力を調整
することが出来る。Alternatively, when the conductance of the connecting portion between the reaction space and the film formation space is small, an appropriate exhaust device is provided in the film formation space,
The pressure in the film forming space can be adjusted by controlling the exhaust amount of the apparatus.
又、反応空間と成膜空間が一体的になつていて、反応位
置と成膜位置が空間的に異なるだけの場合には、前述の
用に差動排気するか或いは、排気能力の充分ある大型の
排気装置を設けてやれば良い。Further, when the reaction space and the film formation space are integrally formed and the reaction position and the film formation position are spatially different from each other, differential evacuation is performed for the above-mentioned purpose or a large evacuation capacity is sufficient. It suffices if an exhaust device is provided.
上記のようにして成膜空間内の圧力は、反応空間に導入
される気体状原料物質と気体状ハロゲン酸化剤の導入圧
力との関係に於いて決められるが、好ましくは０．００
１Torr〜１００Torr、より好ましくは０．０１Torr〜３
０Torr、最適には０．０５〜１０Torrとされるのが望ま
しい。As described above, the pressure in the film formation space is determined by the relationship between the gaseous source material introduced into the reaction space and the introduction pressure of the gaseous halogen oxidant, but preferably 0.00
1 Torr to 100 Torr, more preferably 0.01 Torr to 3
0 Torr, optimally 0.05 to 10 Torr is desirable.
ガスの流型に就いては、反応空間への前記堆積膜形成用
の原料物質、水素ガス及びハロゲン系酸化剤の導入の際
にこれ等が均一に効率良く混合され、前記前駆体Ｅが効
率的に生成され且つ成膜が支障なく適切になされる様
に、ガス導入口と基体とガス排気口との幾何学的配置を
考慮して設計される必要がある。この幾何学的な配置の
好適な例の１つが第１図に示される。Regarding the flow type of gas, when the raw material for forming the deposited film, hydrogen gas and halogen-based oxidant are introduced into the reaction space uniformly and efficiently, the precursor E is efficiently mixed. In order for the gas to be generated and the film to be formed properly without any problem, it is necessary to consider the geometrical arrangement of the gas inlet, the substrate, and the gas outlet. One suitable example of this geometric arrangement is shown in FIG.
成膜時の基体温度（Ts）としては、使用されるガス種及
び形成される堆積膜の種数と要求される特性に応じて、
個々に適宜所望に従つて設定されるが、非晶質の膜を得
る場合には好ましくは室温から450℃、より好ましくは5
0〜400℃とされるのが望ましい。殊に半導体性や光導電
性の特性がより良好なシリコン堆積膜を形成する場合に
は、基体温度（Ts）は70〜350℃とされるのが望まし
い。また、多結晶の膜を得る場合には、好ましくは200
〜650℃、より好ましくは300〜600℃とされるのが望ま
しい。The substrate temperature (Ts) during film formation depends on the type of gas used and the number of types of deposited film to be formed and the required characteristics.
Although individually set as desired, it is preferably room temperature to 450 ° C., more preferably 5 to obtain an amorphous film.
The temperature is preferably 0 to 400 ° C. In particular, when forming a silicon deposited film having better semiconductor properties and photoconductive properties, the substrate temperature (Ts) is preferably 70 to 350 ° C. When a polycrystalline film is obtained, it is preferably 200
It is desirable to set the temperature to 650 ° C, more preferably 300 to 600 ° C.
成膜空間の雰囲気温度（Tat）としては、生成される前
駆体Ｅ及び原子状水素（Ｈ）及び前駆体Ｄが成膜に不適
当な化学種に変化せず、且つ効率良く前駆体Ｅが生成さ
れる様に基体温度(Ts)との関連で適宜所望に応じて決め
られる。As the ambient temperature (Tat) in the film formation space, the generated precursor E, atomic hydrogen (H) and precursor D do not change into chemical species unsuitable for film formation, and the precursor E is efficiently It is appropriately determined as desired in relation to the substrate temperature (Ts) so that it is generated.
本発明に於いて使用される基体としては、形成される堆
積膜の用途に応じて適宜所望に応じて選択されるのであ
れば導電性でも電気絶縁性であつても良い。導電性基体
としては、例えば、NiCr、ステンレス、Al、Cr、Mo、A
u、Nb、Ta、Ｖ、Ti、Pt、Pd等の金属又はこれ等の合金
が挙げられる。The substrate used in the present invention may be conductive or electrically insulating as long as it is appropriately selected according to the intended use of the deposited film to be formed. As the conductive substrate, for example, NiCr, stainless steel, Al, Cr, Mo, A
Examples include metals such as u, Nb, Ta, V, Ti, Pt, and Pd, or alloys thereof.
電気絶縁性基板としては、ポリエステル、ポリエチレ
ン、ポリカーボネート、セルロース、アセテート、ポリ
プロピレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポ
リスチレン、ポリアミド等の合成樹脂のフイルム又はシ
ート、ガラス、セラミツク、紙等が通常使用される。こ
れらの電気絶縁性基体は、好適には少なくともその一方
の表面が導電処理され、該導電処理された表面側に他の
層が設けられるのが望ましい。As the electrically insulating substrate, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, or polyamide, glass, ceramic, paper or the like is usually used. . It is preferable that at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is provided on the surface subjected to the conductive treatment.
例えばガラスであれば、その表面がNiCr、Al、Cr、Mo、
Au、Ir、Nb、Ta、Ｖ、Ti、Pt、Pd、In2O3、SnO2、ITO
（In2O3＋SnO2）等の薄膜を設ける事によつて導電処理
され、或いはポリエステルフイルム等の合成樹脂フイル
ムであれば、NiCr、Al、Ag、Pb、Zn、Ni、Au、Cr、Mo、
Ir、Nb、Ta、Ｖ、Ti、Pt等の金属で真空蒸着、電子ビー
ム蒸着、スパツタリング等で処理し、又は前記金属でラ
ミネート処理して、その表面が導電処理される。支持体
の形状としては、円筒状、ベルト状、板状等、任意の形
状とし得、所望によつて、その形状が決定される。For example, if it is glass, its surface is NiCr, Al, Cr, Mo,
Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In 2 O 3 , SnO 2 , ITO
NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo is used for conductive treatment by providing a thin film of (In 2 O 3 + SnO 2 ) or synthetic resin film such as polyester film. ,
The surface of the metal is subjected to a conductive treatment by treatment with a metal such as Ir, Nb, Ta, V, Ti and Pt by vacuum vapor deposition, electron beam vapor deposition, sputtering or the like, or by laminating with the above metal. The shape of the support may be any shape such as a cylindrical shape, a belt shape, and a plate shape, and the shape is determined as desired.
基体は、基体と膜との密着性及び反応性を考慮して上記
の中より選ぶのが好ましい。更に両者の熱膨張の差が大
きいと膜中に多量の歪が生じ、良品質の膜が得られない
場合があるので、両者の熱膨張の差が近接している基本
を選択して使用するのが好ましい。The substrate is preferably selected from the above in consideration of the adhesion and reactivity between the substrate and the film. Further, if the difference in thermal expansion between the two is large, a large amount of strain may occur in the film, and a good quality film may not be obtained. Therefore, select and use a base whose thermal expansion difference is close to each other. Is preferred.
又、基体の表面状態は、膜の構造（配向）や錐状組織の
発生に直接関係するので、所望の特性が得られる様な膜
構造と膜組織となる様に基体の表面を処理するのが望ま
しい。Further, since the surface condition of the substrate is directly related to the structure (orientation) of the film and the generation of the conical structure, it is necessary to treat the surface of the substrate so that the film structure and the film structure can obtain desired characteristics. Is desirable.
第１図は本発明の堆積膜形成法を実施するに好適な装置
の１例を示すものである。FIG. 1 shows an example of an apparatus suitable for carrying out the deposited film forming method of the present invention.
第１図に示す堆積膜形成装置は、装置本体、排気系及び
ガス供給系の３つに大別される。The deposited film forming apparatus shown in FIG. 1 is roughly divided into three parts: an apparatus main body, an exhaust system and a gas supply system.
装置本体には、反応空間及び成膜空間が設けられてい
る。A reaction space and a film formation space are provided in the apparatus body.
101〜108は夫々、成膜する際に使用されるガスが充填さ
れているボンベ、101ａ〜108ａは夫々ガス供給パイプ、
101ｂ〜108ｂは夫夫各ボンベからのガスの流量調整用の
マスフロ−コントローラー、101ｃ〜108ｃはそれぞれガ
ス圧力計、101ｄ〜108ｄ及び101ｅ〜108ｅは夫々バル
ブ、101ｆ〜108ｆは夫々対応するガスボンベ内の圧力を
示す圧力計である。101 to 108 are cylinders filled with gas used for film formation, 101a to 108a are gas supply pipes,
101b to 108b are mass flow controllers for adjusting the flow rate of gas from each cylinder, 101c to 108c are gas pressure gauges, 101d to 108d and 101e to 108e are valves, and 101f to 108f are inside corresponding gas cylinders. It is a pressure gauge showing the pressure.
120は真空チヤンバーであつて、上部にガス導入用配管
が設けられ、配管の下流に反応空間が形成される構造を
有し、且つ該配管のガス排出口に対向して、基体118が
設置される様に基体ホールダー112が設けられた成膜空
間が形成される構造を有する。ガス導入用の配管は、三
重同心円配置構造となつており、中よりガスボンベ10
1、102よりのガスが導入される第１のガス導入管１０
９、ガスボンベ103〜105よりのガスの導入される第２の
ガス導入管110、及びガスボンベ106〜108よりのガスが
導入される第３のガス導入管111を有する。Reference numeral 120 denotes a vacuum chamber having a structure in which a gas introducing pipe is provided in an upper portion and a reaction space is formed in the downstream of the pipe, and a substrate 118 is installed so as to face a gas discharge port of the pipe. As described above, a film forming space in which the base holder 112 is provided is formed. The gas introduction piping has a triple concentric circle layout structure.
First gas introduction pipe 10 into which gas from 1, 102 is introduced
9, a second gas introduction pipe 110 into which gas from the gas cylinders 103 to 105 is introduced, and a third gas introduction pipe 111 into which gas from gas cylinders 106 to 108 is introduced.
各ガス導入管の反応空間へのガス排出には、その位置が
内側の管になる程基体の表面位置より遠い位置に配され
る設計とされている。即ち、外側の管になる程その内側
にある管を包囲する様に夫々のガス導入管が配設されて
いる。For the gas discharge to the reaction space of each gas introduction pipe, it is designed such that the inner pipe is located farther from the surface position of the substrate. That is, the respective gas introduction pipes are arranged so that the outer pipes surround the inner pipes.
各導入管への管ボンベからのガスの供給は、ガス供給パ
イプライン123〜125によつて夫々なされる。The supply of gas from the pipe cylinders to the respective introduction pipes is performed by gas supply pipelines 123 to 125, respectively.
各ガス導入管、各ガス供給パイプライン及び真空チヤン
バー120は、メイン真空バルブ119を介して不図示の真空
排気装置により真空排気される。Each gas introduction pipe, each gas supply pipeline, and the vacuum chamber 120 are evacuated by a vacuum exhaust device (not shown) via the main vacuum valve 119.
基体118は基体ホルダー112を上下に移動させることによ
つて各ガス導入管の位置より適宜所望の距離に設置され
る。The substrate 118 is set at a desired distance from the position of each gas introduction pipe by moving the substrate holder 112 up and down.
本発明の場合、この基体とガス導入管のガス排出口の距
離は、形成される堆積膜の種類及びその所望される特
性、ガス流量、真空チヤンバーの内圧等を考慮して適切
な状態になる様に決められるが、好ましくは、数mm〜２
０cm、より好ましくは、５mm〜１５cm程度とされるのが
望ましい。In the case of the present invention, the distance between the substrate and the gas outlet of the gas inlet pipe is in an appropriate state in consideration of the type of deposited film to be formed and its desired characteristics, gas flow rate, internal pressure of the vacuum chamber, etc. However, it is preferably several mm to 2
It is preferably 0 cm, more preferably about 5 mm to 15 cm.
113は、基本118を成膜時に適当な温度に加熱したり、或
いは、成膜前に基体118を予備加熱したり、更には、成
膜後、膜をアニールする為に加熱する基体加熱ヒータで
ある。Reference numeral 113 denotes a substrate heating heater that heats the base 118 to an appropriate temperature during film formation, preheats the substrate 118 before film formation, and further heats the film to anneal the film after film formation. is there.
基体加熱ヒータ113は、導線114により導源115により電
力が供給される。Electric power is supplied to the substrate heater 113 from a conductor 115 by a conductor 114.
116は、基体温度（Ts）の温度を測定する為の熱電対で
温度表示装置117に電気的に接続されている。Reference numeral 116 is a thermocouple for measuring the temperature of the substrate temperature (Ts) and is electrically connected to the temperature display device 117.
以下、実施例に従つて、本発明をより具体的に説明する
が、本発明はそれら実施例により限定されるものではな
い。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１ 第１図に示す成膜装置を用いて、次の様にし本発明の方
法による堆積膜を作成した。Example 1 Using the film forming apparatus shown in FIG. 1, a deposited film was prepared by the method of the present invention as follows.
ボンベ101に充填されているSiH4ガスを流量２０sccmで
ガス導入管109より、ボンベ103に充填されているHeで１
０％に希釈したF2ガスを流量200sccmでガス導入管110よ
り、ボンベ107に充填されているH2ガスを流量40sccmで
ガス導入管111より真空チヤンバー102内に導入した。The SiH 4 gas filled in the cylinder 101 is supplied from the gas introduction pipe 109 at a flow rate of 20 sccm to the He in the cylinder 103 by 1
F 2 gas diluted to 0% was introduced into the vacuum chamber 102 at a flow rate of 200 sccm from the gas introduction pipe 110, and H 2 gas filled in the cylinder 107 was introduced at a flow rate of 40 sccm from the gas introduction pipe 111 into the vacuum chamber 102.
このとき、真空チヤンバー120内の圧力を真空バルブ119
の開閉度を調整して400mTorrにした。基体に石英ガラス
（１５cm×１５cm）を用いガス導入口111と基体との距
離は５cmに設定した。SiH4ガスとH2ガスの混合域で青白
い発光が強くみられた。なお、基体の位置は発光部よ２
cm離れている。基体温度(Ts)は各試料に対して表１に示
す様に室温から400℃までの間に設定した。At this time, the pressure in the vacuum chamber 120 is adjusted to the vacuum valve 119.
I adjusted the degree of opening and closing to 400 mTorr. Quartz glass (15 cm × 15 cm) was used as the substrate, and the distance between the gas inlet 111 and the substrate was set to 5 cm. Pale white emission was strongly observed in the mixed region of SiH 4 gas and H 2 gas. The position of the base is 2
cm away. The substrate temperature (Ts) was set between room temperature and 400 ° C. as shown in Table 1 for each sample.
この状態で３０分間ガスを流すと、表１に示す様な膜厚
のSi：Ｈ：Ｆ膜が基体上に堆積した。When the gas was flown for 30 minutes in this state, a Si: H: F film having a film thickness as shown in Table 1 was deposited on the substrate.
又膜厚の分布むらは±５％以内におさまつた。成膜した
Si：Ｈ：Ｆ膜はいずれの試料も電子線回折によつて非晶
質であることが確認された。In addition, the unevenness of the film thickness distribution was settled within ± 5%. Deposited
It was confirmed by electron beam diffraction that each of the Si: H: F films was amorphous.
各試料の非晶質Si：Ｈ：Ｆ膜上にAlのくし形電極（ギヤ
ツプ長200μｍ）を蒸着し、導電率測定用の試料を作成
した。各試料を真空クライオスタツト中にいれ電圧１０
０Ｖを印加し、微少電流計（YHP4140B）で電流を測定
し、暗導電率（σｄ）を求めた。又600nm,0.3mw/cm2の
光を照射し、光導電率（σｐ）を求めた。更に光の吸収
より光学的バンドギヤツプ（Ｅｇopt）を求めた。これ
らの結果は表１に示した。A comb-shaped electrode (gap length 200 μm) of Al was vapor-deposited on the amorphous Si: H: F film of each sample to prepare a sample for conductivity measurement. Put each sample in a vacuum cryostat and apply a voltage of 10
0 V was applied and the current was measured with a micro ammeter (YHP4140B) to obtain the dark conductivity (σd). Further, light having a wavelength of 600 nm and 0.3 mw / cm 2 was irradiated to determine the photoconductivity (σp). Further, the optical bandgap (Eg opt ) was determined from the absorption of light. The results are shown in Table 1.
次に基体温度を300℃に固定し、SiH4の流量を種々かえ
て作成したときの各試料の膜厚、σｄ、σｐ、Egoptの
結果を表２に示す。 Next, Table 2 shows the results of the film thickness, σd, σp, and Eg opt of each sample when the substrate temperature was fixed at 300 ° C. and the flow rate of SiH 4 was changed.
この際ガスを流した時間はいずれの試料も３０分間であ
る。又、いずれの試料もF2ガス流量２sccm、Heガス流量
40sccm、内圧400mTorrとした。At this time, the gas was flown for 30 minutes for all the samples. Also, for all samples, F2 gas flow rate is 2 sccm, He gas flow rate is
The pressure was 40 sccm and the internal pressure was 400 mTorr.
次に、基体温度を300℃、SiH4ガス流量20sccm、F2ガス
流量200sccm、内厚400mTorrとし、H2ガス流量を種々に
変化させて30分間各ガスを流した後に得られた各試料の
膜の膜厚、σｄ，σｐ，Egoptの値を表３に示す。 Next, the substrate temperature was 300 ° C., the SiH 4 gas flow rate was 20 sccm, the F 2 gas flow rate was 200 sccm, and the internal thickness was 400 mTorr, and the H 2 gas flow rate was variously changed, and each gas obtained after flowing each gas for 30 minutes was changed. Table 3 shows the film thickness, σd, σp, and Eg opt values.
次に、基体温度を300℃、SiH4ガス流量20sccm、F2ガス
流量200sccm、H2ガス流量40sccmとし、内圧を種々に変
化させて作成した各試料の膜厚、σｄ，σｐ，Egoptの
値を表４に示す。 Next, the substrate temperature was set to 300 ° C., the SiH 4 gas flow rate was 20 sccm, the F 2 gas flow rate was 200 sccm, and the H 2 gas flow rate was 40 sccm, and the film thickness, σd, σp, and Eg opt of each sample prepared by changing the internal pressure were The values are shown in Table 4.
表１〜表４に示す各試料の膜厚の分布むらはガス導入管
111と基体との距離、ガス導入管109と110及び111に流す
ガス流量、内圧に依存した。各成膜において、ガス導入
管と基体との距離を調整することによつて膜厚の分布む
らは15cm×15cmの基体において、±５％以内におさめる
ことができた。この位置はほとんどの場合発光強度の最
大の位置に対応していた。また成膜したSi：Ｈ：Ｆ膜は
いずれの試料のも、電子線回折の結果によると非晶質で
あることを確認した。 The unevenness of the film thickness of each sample shown in Table 1 to Table 4
It depended on the distance between 111 and the substrate, the gas flow rates flowing through the gas introduction pipes 109, 110 and 111, and the internal pressure. In each film formation, by adjusting the distance between the gas introduction tube and the substrate, the unevenness of the film thickness could be controlled within ± 5% in the substrate of 15 cm × 15 cm. This position almost always corresponded to the position of maximum emission intensity. In addition, it was confirmed that the formed Si: H: F films were amorphous according to the electron diffraction results of all the samples.
実施例２ 実施例１においてHeで10％に希釈したF2ガスを導入する
と共に104ボンベよりCl2ガス（Heガスで10％に希釈）を
導入し、成膜を行なつた。（試料２） このときの成膜条件は次のとおりである。Example 2 In Example 1, F 2 gas diluted with He to 10% was introduced, and Cl 2 gas (diluted to 10% with He gas) was introduced from 104 cylinder to form a film. (Sample 2) The film forming conditions at this time are as follows.
SiH4 20sccm F2 100sccm Cl2 100sccm H2 40sccm 内圧 400mTorr 基体温度 300℃ ガス吹き出し口と基体との距離 5cm 実施例１と同様、SiH4ガスと（F2＋Cl2）ガスとH2ガス
が合流する領域で強い青白い発光がみられた。30分間の
ガス吹き出し後、石英ガラス基体上に約２．０μｍのＡ
−Si：Ｈ：Ｆ：Cl膜が堆積した。SiH 4 20sccm F 2 100sccm Cl 2 100sccm H 2 40sccm Internal pressure 400mTorr Substrate temperature 300 ° C Distance between gas outlet and substrate 5cm Similar to Example 1, SiH 4 gas, (F 2 + Cl 2 ) gas and H 2 gas merge Intense pale-white luminescence was observed in the illuminated area. After blowing out the gas for 30 minutes, about 2.0 μm of A on the quartz glass substrate.
-Si: H: F: Cl film was deposited.
この膜が非晶質であることは電子線回折で確認した。It was confirmed by electron diffraction that the film was amorphous.
該Ａ−Si：Ｈ：Ｆ：Cl膜上にAlのくし形電極（ギヤツプ
長200μｍ）を真空蒸着した後、試料を真空クライオス
タツト中にいれ、暗導電率（σｄ）、600nm、0.3mw/cm2
の光照射時の導電率（σｐ）、及び光学吸収の測定より
光学的バンドギヤツプ（Egopt）を夫々測定した。After vacuum-depositing a comb-shaped electrode (gap length 200 μm) of Al on the A-Si: H: F: Cl film, the sample was placed in a vacuum cryostat and dark conductivity (σd), 600 nm, 0.3 mw / cm 2
The optical bandgap (Eg opt ) was measured by measuring the electrical conductivity (σp) during the light irradiation and the optical absorption.
得られた値は σｄ＝５×１０-11ｓ／cm σｐ＝１×１０-6ｓ／cm Egopt＝1.70eV であつた。The obtained value was σd = 5 × 10 −11 s / cm σp = 1 × 10 −6 s / cm Eg opt = 1.70 eV.
実施例３ 実施例１においてSiH4ガスを導入するかわりに102ボン
ベよりSi2H6ガスを導入し、成膜を行なつた（試例
３）。Example 3 Instead of introducing SiH 4 gas in Example 1, Si 2 H 6 gas was introduced from a 102 cylinder to form a film (Test Example 3).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
Si2H6 20 sccm F2（10％He希釈） 200 sccm H2 40 sccm 内圧 400 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm Si2H6ガスF2ガス及びH2ガスが合流する領域で強い青白
い発光がみられた。10分間のガス吹き出し後、石英ガラ
ス基板上に約1.2μｍのＡ−Si：Ｈ：Ｆ膜が堆積した。Si 2 H 6 20 sccm F 2 (10% He diluted) 200 sccm H 2 40 sccm Internal pressure 400 mTorr Base temperature 300 ℃ Distance between gas outlet and base 5 cm Si 2 H 6 gas F 2 gas and H 2 gas A strong bluish-white emission was observed in the confluence area. After blowing out the gas for 10 minutes, an A-Si: H: F film of about 1.2 μm was deposited on the quartz glass substrate.
この膜が非晶質であることは電子線回折で確認した。It was confirmed by electron diffraction that the film was amorphous.
Ａ−Si：Ｈ：Ｆ膜上にAlのくし形電極（ギヤツプ長200
μｍ）を真空蒸着した後、真空クライオスタツト中にい
れ、暗導電率（σｄ）、600nm、0.3mw/cm2の光照射時の
導電率（σｐ）、及び光学吸収の測定より光学的バンド
ギヤツプ（Egopt）を夫々測定した。Comb-shaped electrode of Al (gear length 200 on A-Si: H: F film)
(μm) in a vacuum cryostat and then placed in a vacuum cryostat to measure the dark conductivity (σd), the conductivity (σp) at 600 nm and 0.3 mw / cm 2 of light, and the optical bandgap ( Eg opt ) was measured respectively.
得られた値は σｄ＝２×１０-10ｓ／cm σｐ＝３×１０-6ｓ／cm Egopt＝1.65eV であつた。The obtained value was σd = 2 × 10 −10 s / cm σp = 3 × 10 −6 s / cm Eg opt = 1.65 eV.
実施例４ 実施例１においてはSiH4ガスを導入するかわりに102ボ
ンベよりGeH4ガスを導入し、成膜を行なつた（試料
４）。Example 4 In Example 1, GeH 4 gas was introduced from a 102 cylinder instead of introducing SiH 4 gas to form a film (Sample 4).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
GeH4 20 sccm F2（10％He希釈） 200 sccm H2 40 sccm 内圧 400 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm このときGeH4ガスとF2ガス及びH2ガスの合流点で青白い
強い発光がみられた。35分間のガス吹き出し後、石英ガ
ラス基板上に約０．８umのＡ−Ge：Ｈ：Ｆ膜が堆積し
た。この膜が非晶質であることは電子線回折で確認し
た。GeH 4 20 sccm F 2 (10% He diluted) 200 sccm H 2 40 sccm Internal pressure 400 mTorr Substrate temperature 300 ℃ Distance between gas outlet and substrate 5 cm At this time, confluence of GeH 4 gas with F 2 gas and H 2 gas A strong pale emission was observed at the dots. After blowing out the gas for 35 minutes, an A-Ge: H: F film of about 0.8 um was deposited on the quartz glass substrate. It was confirmed by electron diffraction that the film was amorphous.
該Ａ−Ge：Ｈ：Ｆ膜上にAlのくし形電極（ギヤツプ長20
0μｍ）を真空蒸着した後、真空クライオスタツト中に
いれ、暗導電率（σｄ）、600nm、0.3mw/cm2の光照射時
の導電率（σｐ）、及び光学吸収の測定より光学的バン
ドギヤツプ（Egopt）を夫々測定した。On the A-Ge: H: F film, a comb-shaped electrode of Al (gear length 20
(0 μm) by vacuum evaporation and then put in a vacuum cryostat to measure the dark conductivity (σd), the conductivity (σp) at 600 nm and 0.3 mw / cm 2 of light irradiation, and the optical bandgap (). Eg opt ) was measured respectively.
得られた値は σｄ＝７×１０-7ｓ／cm σｐ＝５×１０-6ｓ／cm Egopt＝1.1 eV であつた。The obtained value was σd = 7 × 10 −7 s / cm σp = 5 × 10 −6 s / cm Eg opt = 1.1 eV.
実施例５ 実施例１においてはSiH4ガスを導入すると共に、102ボ
ンベよりGeH4ガスを導入し、成膜を行なつた（試料
５）。Example 5 In Example 1, SiH 4 gas was introduced and GeH 4 gas was introduced from a 102 cylinder to form a film (Sample 5).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
SiH4 20 sccm GeH4 5 sccm F2（10％He希釈） 250 sccm H2 50 sccm 内圧 500 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm このときガス吹き出し管の出口近傍において青い強い発
光がみられた。20分間のガス吹き出し後、石英ガラス基
板上に約１．８μｍのＡ−SiGe：Ｈ：Ｆ膜が堆積した。
非晶質であることは電子線回折で確認した。SiH 4 20 sccm GeH 4 5 sccm F 2 (10% He diluted) 250 sccm H 2 50 sccm Internal pressure 500 mTorr Base temperature 300 ℃ Distance between the gas outlet and the base 5 cm At this time, a strong blue color near the outlet of the gas outlet pipe Light emission was observed. After blowing out the gas for 20 minutes, an A-SiGe: H: F film of about 1.8 μm was deposited on the quartz glass substrate.
It was confirmed to be amorphous by electron beam diffraction.
該Ａ−SiGe：Ｈ・Ｆ膜上にAlのくし形電極（ギヤツプ長
200μｍ）を真空蒸着した後、試料５を真空クライオス
タツト中にいれ、暗導電率（σｄ）、600nm、0.3mw/cm2
の光照射時の導電率（σｐ）、及び光学吸収の測定より
光学的バンドギヤツプ（Egopt）を夫々測定した。Comb-shaped electrode of Al (gear length) on the A-SiGe: HF film
(200 μm) after vacuum deposition, put sample 5 in a vacuum cryostat, dark conductivity (σd), 600 nm, 0.3 mw / cm 2
The optical bandgap (Eg opt ) was measured by measuring the electrical conductivity (σp) during the light irradiation and the optical absorption.
得られた値は σｄ＝４×１０-9ｓ／cm σｐ＝８×１０-6ｓ／cm Egopt＝1.4 eV であつた。The obtained value was σd = 4 × 10 -9 s / cm σp = 8 × 10 -6 s / cm Eg opt = 1.4 eV.
実施例６ 実施例５においてGeH4ガスを導入するかわりに102ボン
ベよりC2H4ガスを導入し、成膜を行なつた（試料６）。Example 6 Instead of introducing GeH 4 gas in Example 5, C 2 H 4 gas was introduced from a 102 cylinder to form a film (Sample 6).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
SiH4 20 sccm CeH4 5 sccm F2（10％He希釈） 250 sccm H2 50 sccm 内圧 500 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm 30分間のガス吹き出し後、石英ガラス基体上に約１．０
μｍのＡ−SiC：Ｈ：Ｆ膜が堆積した。この膜が非晶質
であることは電子線回折で確認した。SiH 4 20 sccm CeH 4 5 sccm F 2 (10% He diluted) 250 sccm H 2 50 sccm Internal pressure 500 mTorr Substrate temperature 300 ℃ Distance between gas outlet and substrate 5 cm After blowing gas for 30 minutes, on quartz glass substrate About 1.0
A μm A-SiC: H: F film was deposited. It was confirmed by electron diffraction that the film was amorphous.
該Ａ−SiC：Ｈ：Ｆ膜上にAlのくし形電極（ギヤツプ長2
00μｍ）を真空蒸着した後、試料６を真空クライオスタ
ツト中にいれ、暗導電率（σｄ）、600nm、0.3mw/cm2の
光照射時の導電率（σｐ）、及び光学吸収の測定より光
学的バンドギヤツプ（Egopt）を夫々測定した。Comb-shaped electrode of Al (gear length 2 on the A-SiC: H: F film)
00μm) was vacuum-deposited, and then sample 6 was placed in a vacuum cryostat and measured by dark conductivity (σd), conductivity (σp) at 600nm, 0.3mw / cm 2 light irradiation, and optical absorption. The respective bandgap (Eg opt ) was measured.
得られた値は σｄ＝７×１０-13ｓ／cm σｐ＝２×１０-8ｓ／cm Egopt＝1.9 eV であつた。The obtained value was σd = 7 × 10 -13 s / cm σp = 2 × 10 -8 s / cm Eg opt = 1.9 eV.
実施例７ 実施例１においてSiH4ガスを導入すると共に、102ボン
ベよりSi2H6ガスを導入し、成膜を行なつた（試料
７）。Example 7 SiH 4 gas was introduced in Example 1, and Si 2 H 6 gas was introduced from a 102 cylinder to form a film (Sample 7).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
SiH4 20 sccm Si2H6 5 sccm F2（10％He希釈） 250 sccm H2 50 sccm 内圧 500 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm このときガスの吹き出し口の近傍で青白い強い発光がみ
られた。15分間のガス吹き出し後、石英ガラス基板上に
約１．５μｍのＡ−Si：Ｈ：Ｆ膜が堆積した。この膜が
非晶質であることは電子線回折で確認した。SiH 4 20 sccm Si 2 H 6 5 sccm F 2 (10% He diluted) 250 sccm H 2 50 sccm Internal pressure 500 mTorr Substrate temperature 300 ℃ Distance between gas outlet and substrate 5 cm Near the gas outlet A strong pale emission was observed. After blowing out the gas for 15 minutes, an A-Si: H: F film of about 1.5 μm was deposited on the quartz glass substrate. It was confirmed by electron diffraction that the film was amorphous.
該Ａ−Si：Ｈ：Ｆ膜上にAlのくし形電極（ギヤツプ長20
0μｍ）を真空蒸着した後、試料７を真空クライオスタ
ツト中にいれ、暗導電率（σｄ）、600nm、0.3mw/cm2の
光照射時の導電率（σｐ）、及び光学吸収の測定より光
学的バンドギヤツプ（Egopt）をそれぞれ測定した。On the A-Si: H: F film, a comb-shaped electrode of Al (gear length 20
After vacuum-depositing (0 μm), sample 7 was placed in a vacuum cryostat and measured by dark conductivity (σd), conductivity at 600 nm, 0.3 mw / cm 2 light irradiation (σp), and optical absorption. The respective bandgap (Eg opt ) was measured.
得られた値は σｄ＝８×１０-11ｓ／cm σｐ＝４×１０-6ｓ／cm Egopt＝1.65eV であつた。The obtained value was σd = 8 × 10 -11 s / cm σp = 4 × 10 -6 s / cm Eg opt = 1.65 eV.
実施例８ 実施例７においてF2ガスを導入すると共にCl2をボンベ1
04より導入し、成膜を行なつた（試料８）。Example 8 In Example 7, F 2 gas was introduced and Cl 2 was added to the cylinder 1
It was introduced from 04 and film formation was performed (Sample 8).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
SiH4 20 sccm Si2H6 5 sccm F2（10％He希釈） 150 sccm Cl2 （10％He希釈） 100 sccm H2 50 sccm 内圧 500 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm ガスを流したとき、ガスの合流点で青白い強い発光がみ
られた。15分間のガス吹き出し後、石英ガラス基板上に
約１．５μｍのＡ−Si：Ｈ：Ｆ：Cl膜が堆積した。この
膜が非晶質であることは電子線回折で確認した。SiH 4 20 sccm Si 2 H 6 5 sccm F 2 (10% He diluted) 150 sccm Cl 2 (10% He diluted) 100 sccm H 2 50 sccm Internal pressure 500 mTorr Substrate temperature 300 ℃ Distance between gas outlet and substrate 5 When a cm gas was flowed, a strong pale emission was observed at the confluence of the gases. After blowing out the gas for 15 minutes, an A-Si: H: F: Cl film of about 1.5 μm was deposited on the quartz glass substrate. It was confirmed by electron diffraction that the film was amorphous.
該Ａ−Si：Ｈ：Ｆ：Cl膜上にAlのくし形電極（ギヤツプ
長200μｍ）を真空蒸着した後、試料８を真空クライオ
スタツト中にいれ、暗導電率（σｄ）、600nm、0.3mw/c
m2の光照射時の導電率（σｐ）、及び光学吸収の測定よ
り光学的バンドギヤツプ（Egopt）を測定した。After vacuum-depositing a comb-shaped electrode of Al (gear length 200 μm) on the A-Si: H: F: Cl film, sample 8 was placed in a vacuum cryostat and dark conductivity (σd), 600 nm, 0.3 mw. / c
The optical bandgap (Eg opt ) was measured by measuring the electrical conductivity (σp) at the time of light irradiation of m 2 and the optical absorption.
得られた値は σｄ＝７×１０-11ｓ／cm σｐ＝８×１０-6ｓ／cm Egopt＝1.65eV であつた。The obtained value was σd = 7 × 10 −11 s / cm σp = 8 × 10 −6 s / cm Eg opt = 1.65 eV.
実施例９ 実施例１においてSiH4ガスを導入するかわりに102ボン
ベよりSnH4ガスを導入し、成膜を行なつた（試料９）。Example 9 Instead of introducing SiH 4 gas in Example 1, SnH 4 gas was introduced from a 102 cylinder to form a film (Sample 9).
SnH4 10 sccm F2（10％He希釈） 200 sccm He 40 sccm 内圧 400 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm この際、SnH4ガス、F2ガス、H2ガスの合流点で発光がみ
られた。30分間のガス吹き出し後、石英ガラス基体上に
約０．８μｍのａ−Sn：Ｈ：Ｆ膜が堆積した。電子線回
折で確認したところこの膜は非晶質であることがわかつ
た。SnH 4 10 sccm F 2 (10% He diluted) 200 sccm He 40 sccm Internal pressure 400 mTorr Substrate temperature 300 ℃ Distance between gas outlet and substrate 5 cm At this time, SnH 4 gas, F 2 gas and H 2 gas merge Light emission was observed at the points. After blowing out the gas for 30 minutes, an a-Sn: H: F film of about 0.8 μm was deposited on the quartz glass substrate. When confirmed by electron beam diffraction, it was found that this film was amorphous.
該ａ−Sn：Ｈ：Ｆ膜上にAlのくし形電極（ギヤツプ長20
0μｍ）を真空蒸着した後、実施例１と同様真空クライ
オスタツト中にいれ、暗導電率（σｄ）、及び光学吸収
の測定より光学的バンドギヤツプ（Egopt）を夫々測定
した。On the a-Sn: H: F film, a comb-shaped electrode of Al (gear length 20
(0 μm) was vacuum-deposited and then placed in a vacuum cryostat as in Example 1, and the optical conductivity (σd) and the optical bandgap (Eg opt ) were measured by measuring the optical absorption.
得られた値は σｄ＝２×１０-6ｓ／cm Egopt＝0.80eV であつた。The obtained value was σd = 2 × 10 −6 s / cm Eg opt = 0.80 eV.
実施例１０ 実施例１において基体温度を600℃に設定し、成膜を行
なつた（試料１０）。Example 10 In Example 1, the substrate temperature was set to 600 ° C. and film formation was performed (Sample 10).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
SiH4 20 sccm F2（Heで10％に希釈） 200 sccm H2 100 sccm 内圧 400 mTorr ガス吹き出し口と基体との距離 ５ cm 実施例１と同様、SiH4ガスとF2ガスとH2ガスの合流点で
青い強い発光がみられた。45分間のガス吹き出し後、石
英ガラス基板上に約０．９μｍのSi：Ｈ：Ｆ膜が堆積し
た。堆積膜を電子線回析で測定したところSiの回折ピー
クがみられ、多結晶化していることがわかつた。SiH 4 20 sccm F 2 (diluted to 10% with He) 200 sccm H 2 100 sccm Internal pressure 400 mTorr Distance between gas outlet and substrate 5 cm Similar to Example 1, SiH 4 gas, F 2 gas and H 2 gas A strong blue emission was observed at the confluence point of. After blowing out the gas for 45 minutes, a Si: H: F film of about 0.9 μm was deposited on the quartz glass substrate. When the deposited film was measured by electron diffraction, a diffraction peak of Si was observed and it was found that the film was polycrystallized.
該Si：Ｈ：Ｆ膜上にAlのくし形電極（ギヤツプ長200μ
ｍ）を真空蒸着した後、試料10を真空クライオスタツト
中に入れ、暗導電率（σｄ）、及び光学吸収の測定より
光学的バンドギヤツプ（Egopt）を夫々測定した。A comb-shaped electrode of Al (gear length 200μ on the Si: H: F film)
m) was vacuum-deposited, sample 10 was placed in a vacuum cryostat, and the optical bandgap (Eg opt ) was measured by measuring dark conductivity (σd) and optical absorption.
得られた値は σｄ＝２×１０-3ｓ／cm Egopt＝1.95eV であつた。The obtained value was σd = 2 × 10 −3 s / cm Eg opt = 1.95 eV.
実施例１１ 実施例１においてSiH4ガスを導入すると共に、102ボン
ベよりSnH4ガスを導入し、成膜を行なつた（試料11）。Example 11 SiH 4 gas was introduced in Example 1, and SnH 4 gas was introduced from a 102 bomb to form a film (Sample 11).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
SiH4 20 sccm SnH4 5 sccm F2（10％He希釈） 250 sccm H2 40 sccm 内圧 500 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm このときガス吹き出し管の出口近傍において青い強い発
光がみられた。25分間のガス吹き出し後、石英ガラス基
体上に約１．２μｍのａ−SiSn：Ｈ：Ｆ膜が堆積した。
この膜は非晶質であることは電子線回折で確認した。SiH 4 20 sccm SnH 4 5 sccm F 2 (10% He diluted) 250 sccm H 2 40 sccm Internal pressure 500 mTorr Base temperature 300 ℃ Distance between gas outlet and base 5 cm Blue strong near the outlet of gas outlet Light emission was observed. After blowing out the gas for 25 minutes, an a-SiSn: H: F film of about 1.2 μm was deposited on the quartz glass substrate.
It was confirmed by electron diffraction that this film was amorphous.
該ａ−SiSn：Ｈ：Ｆ膜上にAlのくし形電極（ギヤツプ長
200μｍ）を真空蒸着した後、試料11を真空クライオス
タツト中にいれ、暗導電率（σｄ）、600nm、0.3mw/cm2
の光照射時の導電率（σｐ）、及び光学吸収の測定より
光学的バンドギヤツプ（Egopt）を夫々測定した。A comb-shaped electrode of Al (gear length) on the a-SiSn: H: F film
(200 μm) by vacuum evaporation, and then put sample 11 in a vacuum cryostat, dark conductivity (σd), 600 nm, 0.3 mw / cm 2
The optical bandgap (Eg opt ) was measured by measuring the electrical conductivity (σp) during the light irradiation and the optical absorption.
得られた値は σｄ＝４×１０-8ｓ／cm σｐ＝８×１０-7ｓ／cm Egopt＝1.2eV であつた。The obtained value was σd = 4 × 10 -8 s / cm σp = 8 × 10 -7 s / cm Eg opt = 1.2 eV.
実施例１２ 実施例１においてSiH4ガスの代りに、Al2(CH3)6ガスが
充填されたボンベを102ガスボンベのつなぎ口、Al2(C
H3)6をHeガスでバブリングして流し成膜を行なつた（試
料12）。バブリング温度は60℃とした。Example In 12 Example 1 in place of the SiH 4 gas, Al 2 (CH 3) a bomb 6 gas-filled 102 gas cylinder connecting port, Al 2 (C
H 3 ) 6 was bubbled with He gas to flow to form a film (Sample 12). The bubbling temperature was 60 ° C.
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
Al2(CH3)をバブリングしたときのHe流量 20 sccm F2（10％He希釈） 200 sccm H2流量 40 sccm 内圧 400 mTor
r 基体温度 室温 基体 石英基体 ガス吹き出し口と基体との距離 5 cm このとき、ガス吹き出し口の出口近傍から基体にかけて
発光がみられた。He flow rate when Al 2 (CH 3 ) is bubbled 20 sccm F 2 (10% He diluted) 200 sccm H 2 flow rate 40 sccm Internal pressure 400 mTor
r Substrate temperature Room temperature Substrate Quartz substrate Distance between gas outlet and substrate 5 cm At this time, light emission was observed from the vicinity of the outlet of the gas outlet to the substrate.
10分間のガス吹き出し後、石英基体上に2000ÅのAlの膜
が堆積していた。After the gas was blown for 10 minutes, a 2000 Å Al film was deposited on the quartz substrate.
導電率は真空蒸着で作成したAlとほとんど変わらなかつ
た。また石英基体への密着性は、真空蒸着したAl膜に比
べ著しく良好であつた。The conductivity was almost the same as that of Al prepared by vacuum evaporation. The adhesion to the quartz substrate was significantly better than that of the vacuum-deposited Al film.
実施例１３ 実施例１において、SiH4ガスの代りにＷ(ＣＯ)6ボンベ
を102ガスボンベとした。そしてＷ(ＣＯ)6をHeガスでバ
ブリングして流し、成膜を行なつた。Example 13 In Example 1, a W (CO) 6 cylinder was used as the 102 gas cylinder instead of the SiH 4 gas. Then, W (CO) 6 was bubbled with He gas to flow to form a film.
（試料13）。バブリング温度は60℃とした。(Sample 13). The bubbling temperature was 60 ° C.
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
W(CO)6をバブリングしたときのHe流量 20sccm F2（10％希釈） 200 sccm H2流量 40 sccm 内圧 400 mTorr 基体温度 室温 基体 石英基体 ガス吹き出し口と基体との距離 5cm このときガス吹き出し口の出口近傍から基体にかけて発
光がみられた。He flow rate when W (CO) 6 is bubbled 20 sccm F 2 (10% dilution) 200 sccm H 2 flow rate 40 sccm Internal pressure 400 mTorr Substrate temperature Room temperature Substrate Quartz substrate Distance between gas outlet and substrate 5 cm Gas outlet at this time Light emission was observed from the vicinity of the exit of the substrate to the substrate.
20分間のガス吹き出し後、石英基体上に3500ÅのＷ膜が
堆積していた。導電率は電子ビーム真空蒸着で作成した
Ｗ膜と殆ど変わらなかつた。又石英基体への密着性は、
電子ビーム蒸着で得たＷ膜に比べ著しく良好であつた。After blowing out the gas for 20 minutes, a 3500Å W film was deposited on the quartz substrate. The conductivity was almost the same as that of the W film formed by electron beam vacuum evaporation. Also, the adhesion to the quartz substrate is
It was significantly better than the W film obtained by electron beam evaporation.
実施例１４ 実施例１においてSiH4ガスを流す代りに、H2Seガスを流
して、成膜を行なつた（試料14）。Example 14 Instead of flowing SiH 4 gas in Example 1, H 2 Se gas was caused to flow to form a film (Sample 14).
このときの成膜条件は次のとおりである。The film forming conditions at this time are as follows.
H2Se 20 sccm F2（10％He希釈） 200 sccm H2 40 sccm 内圧 500 mTorr 基体温度 60 ℃ 基体 石英基体 ガス吹き出し口と基体との距離 ５ cm ガスを流すと、ガス吹き出し管の出口近傍より基板にか
けて発光がみられた。H 2 Se 20 sccm F 2 (10% He diluted) 200 sccm H 2 40 sccm Internal pressure 500 mTorr Substrate temperature 60 ℃ Substrate Quartz substrate Distance between gas outlet and substrate 5 cm When gas is flowed, near gas outlet Further, light emission was observed over the substrate.
20分間のガス吹き出し後、石英基板上に約１．５μｍの
Se膜が堆積していた。After blowing out the gas for 20 minutes, deposit about 1.5 μm on the quartz substrate.
Se film was deposited.
得られたSe膜は電子線回折の結果、非晶質であることを
確認した。Se膜上に、真空蒸着法でくし形のAl電極を蒸
着して、実施例１に記載した方法で暗導電率（σｄ）、
600nm、0.3mw/cm2の光照射時の導電率（σｐ）、及び光
学吸収の測定より光学的バンドギヤツプ（Egopt）を測
定した。As a result of electron diffraction, the obtained Se film was confirmed to be amorphous. A comb-shaped Al electrode was deposited on the Se film by a vacuum deposition method, and the dark conductivity (σd) was measured by the method described in Example 1.
The optical bandgap (Eg opt ) was measured by measuring the electrical conductivity (σp) when irradiated with light of 600 nm and 0.3 mw / cm 2 , and the optical absorption.
得られた値は σｄ＝６×１０-13ｓ／cm σｐ＝４×１０-8ｓ／cm Egopt＝1.8 eV であつた。The obtained value was σd = 6 × 10 -13 s / cm σp = 4 × 10 -8 s / cm Eg opt = 1.8 eV.
実施例１５ 実施例１においてF2を導入する代りに、104ボンベよりC
l2ガスを導入し、成膜を行なつた（試料15）。Example 15 Instead of introducing F 2 in Example 1, C was obtained from 104 cylinders.
A film was formed by introducing l 2 gas (Sample 15).
このときの成膜条件は次のとおりであつた。The film forming conditions at this time were as follows.
SiH4 20 sccm Cl2（He で10％に希釈） 200 sccm H2 40 sccm 内圧 400 mTorr 基体温度 300 ℃ ガス吹き出し口と基体との距離 ５ cm この際、SiH4ガスとCl2ガスが合流する点で強い発光が
みられた。30分間のガス吹き出し後、石英ガラス基板上
に約１．３μｍ厚のａ−Si：Ｈ：Cl膜が堆積した。この
膜が非晶質であることは電子線回折で確認した。SiH 4 20 sccm Cl 2 (diluted to 10% with He) 200 sccm H 2 40 sccm Internal pressure 400 mTorr Substrate temperature 300 ℃ Distance between gas outlet and substrate 5 cm At this time, SiH 4 gas and Cl 2 gas join together Strong light emission was observed at the points. After blowing out the gas for 30 minutes, an a-Si: H: Cl film having a thickness of about 1.3 μm was deposited on the quartz glass substrate. It was confirmed by electron diffraction that the film was amorphous.
該ａ−Si：Ｈ：Cl膜上にAlのくし形電極（ギヤツプ長20
0μｍ）を真空蒸着した後、試料15を真空クライオスタ
ツト中にいれ、暗導電率（σｄ）、600nm、0.3mw/cm2の
光照射時の導電率（σｐ）、及び光学吸収の測定より光
学的バンドギヤツプ（Egopt）を測定した。On the a-Si: H: Cl film, a comb electrode of Al (gear length 20
Sample 15 was placed in a vacuum cryostat after vacuum evaporation (0 μm), and measured by dark conductivity (σd), conductivity at 600 nm, 0.3 mw / cm 2 light irradiation (σp), and optical absorption. The static bandgap (Eg opt ) was measured.
得られた値は σｄ＝３×１０-11ｓ／cm σｐ＝２×１０-7ｓ／cm Egopt＝1.65eV であつた。The obtained value was σd = 3 × 10 -11 s / cm σp = 2 × 10 -7 s / cm Eg opt = 1.65 eV.
以上の詳細な説明及び各実施例より、本発明の堆積膜形
成法によれば、省エネルギー化を計ると同時に膜品質の
管理が容易で大面積に亘つて均一物理特性の堆積膜が得
られる。又、生産性、量産性に優れ、高品質で電気的、
光学的、半導体的等の物理特性に優れた膜を簡便に得る
ことが出来る。From the above detailed description and each example, according to the deposited film forming method of the present invention, it is possible to obtain a deposited film having a uniform physical property over a large area while achieving energy saving and easy control of film quality. In addition, it has excellent productivity and mass productivity, high quality and electrical,
A film having excellent physical properties such as optical properties and semiconductor properties can be easily obtained.
第１図は本発明の実施例に用いた成膜装置の模式的概略
図である。 図において、 101〜108……ガスボンベ 101a〜108a……ガスの導入管 101b〜108b……マスフロメーター 101c〜108c……ガス圧力計 101d〜108d及び101e〜108e……バルブ 101f〜108f……圧力計 109、110、111……ガス導入管 112……基体ホルダー 113……基体加熱用ヒーター 116……基体温度モニター用熱電対 118……基体、119……真空排気バルブFIG. 1 is a schematic diagram of a film forming apparatus used in an example of the present invention. In the figure, 101-108 ... Gas cylinder 101a-108a ... Gas introduction pipe 101b-108b ... Mass flow meter 101c-108c ... Gas pressure gauge 101d-108d and 101e-108e ... Valve 101f-108f ... Pressure 109, 110, 111 …… Gas inlet pipe 112 …… Base holder 113 …… Heater for heating base 116 …… Thermocouple for monitoring base temperature 118 …… Base, 119 …… Vacuum exhaust valve
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０１Ｌ 21/205 31/04 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location H01L 21/205 31/04
Claims (18)
スと、該原料物質に酸化作用をする性質を有する気体状
ハロゲン系酸化剤とを反応空間内に導入して化学的に接
触させることで励起状態の前駆体原子状水素を含む複数
の前駆体を生成し、これらの前駆体の内少なくとも１つ
の前駆体を堆積膜構成要素の供給源として成膜空間内に
ある基体上に堆積膜を形成することを特徴とする堆積膜
形成法。1. A gaseous source material for forming a deposited film, hydrogen gas, and a gaseous halogen-based oxidizer having a property of oxidizing the source material are introduced into a reaction space and chemically contacted with each other. In this way, a plurality of precursors containing excited state atomic hydrogen are generated, and at least one of these precursors is used as a source of the deposited film component on the substrate in the film formation space. A deposited film forming method characterized by forming a deposited film.
に記載の堆積膜形成法。2. The method for forming a deposited film according to claim 1, wherein light is emitted during generation.
である特許請求の範囲第１項に記載の堆積膜形成法。3. The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain silane compound.
合物である特許請求の範囲第３項に記載の堆積膜形成
法。4. The deposited film forming method according to claim 3, wherein the chain silane compound is a straight chain silane compound.
2n+2（ｎは１〜８の整数）で示される特許請求の範囲第
４項に記載の堆積膜形成法。5. The linear silane compound has the general formula SinH.
The deposited film forming method according to claim 4, which is represented by 2n + 2 (n is an integer of 1 to 8).
ン化合物である特許請求の範囲第３項に記載の堆積膜形
成法。6. The deposited film forming method according to claim 3, wherein the chain silane compound is a branched chain silane compound.
有するシラン化合物である特許請求の範囲第１項に記載
の堆積膜形成法。7. The deposited film forming method according to claim 1, wherein the gaseous raw material is a silane compound having a silicon ring structure.
物である特許請求の範囲第１項に記載の堆積膜形成法。8. The deposited film forming method according to claim 1, wherein the gaseous raw material is a chain germane compound.
2m+2（ｍは１〜５の整数）で示される特許請求の範囲第
８項に記載の堆積膜形成法。9. The chain germane compound has the general formula Ge m H
The deposited film forming method according to claim 8, which is represented by 2m + 2 (m is an integer of 1 to 5).
物である特許請求の範囲第１項に記載の堆積膜形成法。10. The deposited film forming method according to claim 1, wherein the gaseous raw material is a tin hydride compound.
系化合物である特許請求の範囲第１項に記載の堆積膜形
成法。11. The deposited film forming method according to claim 1, wherein the gaseous raw material is a tetrahedral compound.
ンガスを含む特許請求の範囲第１項に記載の堆積膜形成
法。12. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains a halogen gas.
スを含む特許請求の範囲第１項に記載の堆積膜形成法。13. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains fluorine gas.
スを含む特許請求の範囲第１項に記載の堆積膜形成法。14. The deposited film forming method according to claim 1, wherein the gaseous halogen-based oxidizing agent contains chlorine gas.
子を構成成分として含むガスである特許請求の範囲第１
項に記載の堆積膜形成法。15. The gas-based halogen-based oxidizing agent is a gas containing a fluorine atom as a constituent.
The method for forming a deposited film according to item.
状態のハロゲンを含む特許請求の範囲第１項に記載の堆
積膜形成法。16. The method for forming a deposited film according to claim 1, wherein the gaseous halogen-based oxidizing agent contains halogen in a nascent state.
ガスと前記気体状ハロゲン系酸化剤の前記反応空間への
導入方向に対して対向する位置に配設される特許請求の
範囲第１項に記載の堆積膜形成法。17. The substrate according to claim 1, wherein the substrate is arranged at a position opposed to a direction in which the gaseous raw material, hydrogen gas, and the gaseous halogen-based oxidant are introduced into the reaction space. The method for forming a deposited film according to item.
体状ハロゲン系酸化剤は前記反応空間へ、多重管構造の
輸送管から導入される特許請求の範囲第１項に記載の堆
積膜形成法。18. The deposited film formation according to claim 1, wherein the gaseous source material, hydrogen gas and the gaseous halogen-based oxidant are introduced into the reaction space through a transport pipe having a multi-tubular structure. Law.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61040333A JPH0647734B2 (en) | 1986-02-27 | 1986-02-27 | Deposited film formation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61040333A JPH0647734B2 (en) | 1986-02-27 | 1986-02-27 | Deposited film formation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62199771A JPS62199771A (en) | 1987-09-03 |
| JPH0647734B2 true JPH0647734B2 (en) | 1994-06-22 |
Family
ID=12577695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61040333A Expired - Lifetime JPH0647734B2 (en) | 1986-02-27 | 1986-02-27 | Deposited film formation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0647734B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7678420B2 (en) * | 2005-06-22 | 2010-03-16 | Sandisk 3D Llc | Method of depositing germanium films |
| JP4990594B2 (en) * | 2006-10-12 | 2012-08-01 | 東京エレクトロン株式会社 | Gas supply apparatus, gas supply method, thin film forming apparatus cleaning method, thin film forming method, and thin film forming apparatus |
| US20090074962A1 (en) * | 2007-09-14 | 2009-03-19 | Asml Netherlands B.V. | Method for the protection of an optical element of a lithographic apparatus and device manufacturing method |
| JP5663488B2 (en) * | 2009-10-14 | 2015-02-04 | 大陽日酸株式会社 | Method and apparatus for supplying hydrogen selenide mixed gas for solar cell |
-
1986
- 1986-02-27 JP JP61040333A patent/JPH0647734B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62199771A (en) | 1987-09-03 |
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